Beruflich Dokumente
Kultur Dokumente
An in situ derivatization solid-phase microextraction (such as dose of chlorine and free chlorine contact time).1 In the
method has been developed for the determination of early days of DBP research, trihalomethanes (THMs) received
haloacetic acids (HAAs) in water. The analytical procedure almost exclusive attention, because chloroform was shown to be
involves derivatization of HAAs to their methyl esters with an animal carcinogen. However, awareness that HAAs present
dimethyl sulfate, headspace sampling using solid-phase serious human health hazards has increased. The U.S. Environ-
microextraction (SPME), and gas chromatography-ion mental Protection Agency (USEPA) has classified dichloroacetic
trap mass spectrometry (GC/ITMS) determination. Pa- acid as a group B2, probable human carcinogen, on the basis of
rameters affecting both derivatization efficiency and head- positive carcinogenic findings in the liver of two animal species,
space SPME procedure, such as the selection of the male B6C3F1 mouse2 and male rats,3 and trichloroacetic acid as a
SPME coating, derivatization-extraction time and tem- group C, possible human carcinogen, on the basis of limited
perature, and ionic strength, were optimized. The com- evidence of carcinogenicity to the liver in animals.2,4 Accordingly,
mercially available Carboxen-poly(dimethylsiloxane) (CAR- in the first stage of the D/DBP rule, the USEPA has established
PDMS) fiber appears to be the most suitable for the a maximum contamination level (MCL) of 60 µg/L for the sum
determination of HAAs. Moreover, the formation of HAA of five HAAs: monochloroacetic acid, dichloroacetic acid, trichlo-
methyl esters was dramatically improved (up to 90-fold) roacetic acid, monobromoacetic acid, and dibromoacetic acid.5
by the addition of tetrabutylammonium hydrogen sulfate Under stage II of this rule, this MCL is expected to be reduced
(4.7 µmol) to the sample as ion-pairing agent in the to 30 µg/L. Consequently, efforts must be made to develop fast
derivatization step. The precision of the in situ derivati- and accurate analytical methods of monitoring concentration,
zation/HS-SPME/GC/ITMS method evaluated using an behavior, and distribution of HAAs in water.
internal standard gave relative standard deviations (RSDs) Most of the methods used to determine HAAs involve gas
between 6.3 and 11.4%. The method was linear over 2 chromatography (GC) with electron capture detection (ECD) or
orders of magnitude, and detection limits were compound- coupled with mass spectrometry (GC/MS). For the analysis of
dependent, but ranged from 10 to 450 ng/L. The method these compounds by GC, a prior derivatization step is necessary
was compared with the EPA method 552.2 for the because of their low volatility and high polarity. Liquid-solid or
analysis of HAAs in various water samples, and good liquid-liquid extraction (LLE) is commonly used for the isolation
agreement was obtained. Consequently, in situ derivati- of HAAs. After an extraction step, the derivatization of HAAs to
zation/HS-SPME/GC/ITMS is proposed for the analysis short-chain esters using different reagents, such as diazomethane,6
of HAAs in water. acid-alcohol,7,8 or BF3-methanol,9 is often applied. Other authors
(1) Minear, R. A.; Amy, G. L. Water Disinfection and Natural Organic Matter:
Chemical oxidants, such as chlorine, ozone, chloramines, Characterization and Control; ACS Symposium Series 649; American Chemi-
cal Society: Washington, DC, 1996.
chlorine dioxide, etc., are used in the treatment of drinking water (2) Bull, J. R.; Sanchez, I. M.; Nelson, M. A.; Larson, J. L.; Lansing, A. J.
in many parts of the world, mostly for disinfection and removal Toxicology 1990, 63, 341-359.
of obnoxious chemical compounds or potential toxicants. However, (3) DeAngelo, A. B.; Daniel, F. B.; Most, B. M.; Olson, G. R. Toxicology 1996,
114, 207-221.
water treatment practices also generate disinfection byproducts (4) DeAngelo, A. B.; Daniel, F. B.; Most, B. M.; Olson, G. R. J. Toxicol. Environ.
(DBPs) due to reactions of these oxidants with natural organic Health 1997, 52, 425-445.
matter present in water. Nowadays, the most common drinking (5) U.S. Environmental Protection Agency (USEPA); Disinfectants and Disinfec-
tion Byproducts: Proposed Rule; Fed. Reg. 59:38668-38829; Washington, DC,
water disinfectant worldwide is chlorine, which produces triha- 1994.
lomethanes (THMs) and haloacetic acids (HAAs) as the most (6) Heller-Grossman, L.; Manka, J.; Limoni-Relis, B.; Rebhun, M. Water Res.
prevalent groups of chlorination byproducts. The levels and 1993, 27, 1323-1331.
(7) Methods for the determination of Organic Compounds in Drinking Water.
speciation of these compounds depend on the water quality Supplement III. Determination of Organic Compounds in Drinking Water by
conditions (such as total organic content, bromide concentration, Liquid-Liquid Extraction, Derivatization and Gas Chromatography with
temperature, and pH), as well as on the disinfection conditions Electron Capture Detection; Method 552.2, EPA/600/R-95/131; U.S. Envi-
ronmental Protection Agency, Environmental Monitoring Systems Labora-
tory: Cincinnati, OH, 1995.
* Corresponding author: (e-mail) galceran@zeus.qui.ub.es; (fax) +34 93 402 (8) Reimann, S.; Grob, K.; Frank, H. Environ. Sci. Technol. 1996, 30, 2340-
12 33. 2344.
10.1021/ac000479d CCC: $19.00 © 2000 American Chemical Society Analytical Chemistry, Vol. 72, No. 20, October 15, 2000 4865
Published on Web 09/14/2000
proposed simultaneous extraction-derivatization10 or a derivati- described the analysis of HAAs in drinking water by in situ acidic
zation step prior to the extraction.8,11,12 The derivatization is derivatization to the methyl esters with HCl/methanol followed
performed either in dry conditions by evaporation of the matrix by headspace SPME (HS-SPME) and GC-ECD determination
sample or directly in water, and in both cases the derivatives are using a poly(dimethylsiloxane) fiber. Although this method is
then extracted by organic solvents8,11 or directly analyzed by the rapid, a high limit of detection was obtained for monochloroacetic
headspace technique.12 On the other hand, the Grob closed-loop acid (400 µg/L) and only three chlorinated acetic acids were
stripping analysis (CLSA) technique has recently been employed studied. More recently, a new method for the analysis of the six
for the determination of the most common nonpolar and polar HAAs included in EPA method 552 using HS-SPME/GC coupled
halogenated DBPs using GC-ECD analysis, but only results for to ion-trap mass spectrometry (ITMS) was developed in our
dichloroacetic acid and dibromoacetic acid have been reported.13 laboratory.32 Acid-catalyzed ethylation instead of methylation was
Determination of HAAs without derivatization is possible by using used to form volatile esters with high partition constants on the
liquid chromatography,6,14-16 especially ion chromatography15,16 fiber in order to obtain low detection limits. The method showed
or capillary zone electrophoresis.17 Some of these methods are good sensitivity (detection limits from 10 to 200 ng/L), but was
able to achieve detection limits for HAAs similar to or even better relatively time- and labor-intensive.
than GC methods, but multistep procedures, involving trace In this paper, a new method for analysis of HAAs in water using
enrichment processes, are also necessary, which is tedious and HS-SPME/GC/ITMS is proposed. Direct derivatization of HAAs
time-consuming. in water by dimethyl sulfate or diethyl sulfate was tested in order
Solid-phase microextraction (SPME), pioneered by Pawliszyn to obtain low detection limits, to avoid tedious preconcentration
and co-workers,18-20 is a rapidly growing technique. It involves steps, and to reduce the analysis time. Experimental conditions
the partitioning of organic analytes from the aqueous or gaseous to obtain high efficiency in the derivatization step were established
medium onto the stationary-phase coating of a SPME fiber. The and HS-SPME parameters were optimized to achieve good
analytes can be determined by GC via thermal desorption at the sensitivity in the GC. The optimized procedure was applied to the
GC injector port, or by HPLC via a special interface. SPME has analysis of nine HAAs (EPA method 552.2) in tap water and
been used successfully for the analysis of a wide range of organic swimming-pool water.
compounds in water samples,21,22 and recently, it has been applied
for the determination of various DBPs in water samples, such as EXPERIMENTAL SECTION
trihalomethanes and halogenated solvents,23-25 iodinated halo- Chemicals and Materials. Monochloroacetic acid (MCAA,
methanes,26,27 carbonyl compounds,28 cyanogen halides,29 and also 99%), monobromoacetic acid (MBAA, 99%), dichloroacetic acid
for compounds causing taste and odor in water supplies, such as (DCAA, 99%), dibromoacetic acid (DBAA, 98%), trichloroacetic
geosmin and 2-methylisoborneol.30 To our knowledge, only two acid (TCAA, 99.5%), and tribromoacetic acid (TBAA, 99%) were
studies report HAAs analysis by SPME. Aikawa and co-workers31 obtained from Fluka (Buchs, Switzerland); bromodichloroacetic
(9) Boucharat, C.; Desauziers, V.; Le Cloirec, P. Talanta 1998, 47, 311-323.
acid (BDCAA, 99%) and chlorodibromoacetic acid (CDBAA, 99%)
(10) Benanou, D.; Acobas, F.; Sztajnbok, P. Water Res. 1998, 32, 2798-2806. were purchased from Supelco (Bellefonte, PA), and finally,
(11) Scott, B. F.; Alaee, M. Water Qual. Res. J. Can. 1998, 33, 279-293. bromochloroacetic acid (BCAA, 98%) was supplied by Chem
(12) Neitzel, P. L.; Walther, W.; Nestler, W. Fresenius’ J. Anal. Chem. 1998,
361, 318-323.
Service (West Chester, PA). All standards were used as received.
(13) Kampioti, A. A.; Stephanou, E. G. J. Chromatogr., A 1999, 857, 217-229. A commercially available EPA 552.2 esters calibration mixture in
(14) Hashimoto, S.; Otsuki, J. J. High Resolut. Chromatogr. 1998, 21, 55-58. methyl tert-butyl ether (MtBE), containing the methyl esters of
(15) Sarzanini, C.; Bruzzoniti, M. C.; Mentasti, E. J. Chromatogr., A 1999, 850,
197-211
the 9 HAAs at a purity higher than 97% and concentrations
(16) Lopez-Avila, V.; Liu, Y.; Charan, C. J. AOAC Int. 1999, 82, 689-704. between 200 and 2000 µg/mL, was obtained from Supelco
(17) Martı́nez, D.; Borrull, F.; Calull, M. J. Chromatogr., A 1999, 835, 187-196. (Bellefonte, PA). The derivatization reagents dimethyl sulfate
(18) Arthur, C. L.; Killam, L. M.; Buchholz, K. D.; Pawliszyn, J. Anal. Chem.
1992, 64, 1960-1966.
(DMS) and diethyl sulfate (DES), as well as the ion-pairing agent,
(19) Zhang, Z.; Pawliszyn, J. Anal. Chem. 1993, 65, 1843-1852. tetrabutylammonium hydrogen sulfate (TBA-HSO4), and the
(20) Pawliszyn, J. Solid-Phase Microextraction: Theory and Practice; Wiley-VCH: dechlorinating agent, ammonium chloride, were obtained from
New York, 1997.
(21) Eisert, R.; Levsen, K. J. Chromatogr., A 1996, 733, 143-157.
Fluka at a high purity (g99%). The derivatization reagents, as well
(22) Pawliszyn, J. Applications of Solid-Phase Microextraction; RSC Chromatog- as some HAAs are carcinogenic or toxic and were handled in
raphy Monographs: Cambridge, 1999. accordance with the most current material safety data sheets. The
(23) Nilsson, T.; Pelusio F.; Montanarella L.; Larsen B.; Facchetti, S.; Madsen,
J. O. J. High Resolut. Chromatogr. 1995, 18, 617-624.
compounds, 2,3-dibromopropionic acid (98%) and 1,2-dibromopro-
(24) Popp, P.; Paschke, A. Chromatographia 1997, 46, 419-424. pane (97%), used as the surrogate standard and internal standard
(25) Apfalter, S.; Krska R.; Linsinger, T.; Oberhauser, A.; Kandler, W.; Grasser- were purchased from Fluka and Sigma-Aldrich (Milwaukee, WI).
bauer, M. Fresenius’ J. Anal. Chem. 1999, 364, 660-665.
(26) Frazey, P. A.; Barkley, R. M.; Sievers, R. E. Anal. Chem. 1998, 70, 638-
Methanol of residue analysis grade and sulfuric acid for analysis
644. were supplied by Merck (Darmstadt, Germany), whereas MtBE
(27) Cancho, B.; Ventura, F.; Galceran, M. T. J. Chromatogr., A 1999, 841, 197- of residue analysis grade was obtained from Fluka. Anhydrous
206.
(28) Bao, M.; Pantani, F.; Griffini, O.; Burrini, D.; Santianni, D.; Barbieri, K. J.
sodium sulfate and copper (II) sulfate pentahydrate were pur-
Chromatogr., A 1998, 809, 75-87. chased from Panreac (Barcelona, Spain) and Probus (Badalona,
(29) Cancho, B.; Ventura, F.; Galceran, M. T. submitted to J. Chromatogr., A. Spain), respectively. Water from the Milli-Q water purification
Departament of Organic Analytical Chemistry. Societat General d’Aigües
de Barcelona, S. A. Barcelona, 1999.
system (Millipore Corp., Bedford, MA) was used.
(30) McCallum, R.; Pendleton, P.; Schumann, R.; Trinh, M.-U. Analyst (Cambridge,
U. K.) 1998, 123, 2155-2160. (32) Sarrión, M. N.; Santos, F. J.; Galceran, M. T. J. Chromatogr., A 1999, 859,
(31) Aikawa, B.; Burk, R. C. Int. J. Environ. Anal. Chem. 1997, 66, 215-224. 159-171.
4866 Analytical Chemistry, Vol. 72, No. 20, October 15, 2000
SPME experiments were performed with a manual fiber holder reference. The transfer line and the ion trap manifold temperatures
supplied from Supelco (Bellefonte, PA). Five commercially avail- were maintained at 270 and 220 °C, respectively. For ethylation
able fibers, Poly(dimethylsiloxane), PDMS, 100 µm; Polyacrylate, experiments, the instrument was operated in full-scan mode and
PA, 85 µm; Carboxen-Poly(dimethylsiloxane), CAR-PDMS, 75 µm; the mass range was from m/z 27 to 325 at 0.8 s/scan. For
Poly(dimethylsiloxane)-divinylbenzene, PDMS-DVB, 65 µm; and quantification, two selected ions of each ethyl haloacetate were
StableFlex Divinylbenzene-Carboxen-Poly(dimethylsiloxane), DVB- monitored: m/z 77/94 for MCAA, 83/85 for DCAA, 117/82 for
CAR-PDMS, 50/30 µm were purchased from Supelco. Before use, TCAA, 121/138 for MBAA, 174/120 for DBAA, 251/172 for TBAA,
each fiber was conditioned in a heated GC split/splitless injection 129/109 for BCAA, 163/161 for BDCAA, and 209/205 for CDBAA.
port under helium flow according to the manufacturer’s instruc- For methylation experiments, the mass spectrometer was operated
tions. Screw-capped vials (10, 30, and 40 mL), sealed with a Teflon- in full-scan mode between m/z 29 and 260 at 0.8 s/scan, with an
lined silicon septum and used for storing the standard solutions ionization time of 100 ms. After establishing the optimized
as well as for sample derivatization and extraction in both HS- conditions, different acquisition segments during each chromato-
SPME and LLE procedures, were obtained from Wheaton (Millville, graphic run were applied using a narrow mass range and different
NJ). The vials were cleaned with AP-13 Extran alkaline soap scan rates. To enhance the response, ionization times of 200 or
(Merck) for 24 h; rinsed consecutively with (i) deionized water, 400 ms, depending on the compound, were used. The ions of the
(ii) 1:10 HCl/water, (iii) again with deionized water, and (iv) finally methyl haloacetates used for quantification were as follows: m/z
with Milli-Q water; and baked at 110 °C overnight. Volumetric 59/108 for MCAA, 83/85 for DCAA, 117/119 for TCAA, 93/95
glassware was washed as described above, but was air-dried. for MBAA, 173/171 for DBAA, 251/253 for TBAA, 129/127 for
Anhydrous sodium sulfate was heated to 400 °C overnight to BCAA, 163/161 for BDCAA, and 209/205 for CDBAA. For MCAA
remove phthalates and other interfering organic substances and m/z 59 instead of 77 was used to prevent interference from the
then stored at 110 °C until use. fiber. Saturn version 5.2 software was used for data acquisition.
Stock standard solutions of each HAA (2000 µg/mL) were Analyses of HAAs by EPA method 552.2 were performed on a
prepared by weight in Milli-Q water. Standard mixtures were Carlo Erba 5300 Mega Series gas chromatograph (Milan, Italy),
prepared weekly or daily, depending on their concentration, except equipped with a 63Ni electron capture detector (ECD). A 60 m ×
for TBAA, which was prepared daily because it decomposes 0.25 mm i.d. × 0.25 µm DB-1701 fused-silica capillary column
spontaneously at 25 °C.6 All solutions were stored frozen in the (J&W Scientific, Folsom, CA) was used. The column temperature
dark at -17 °C until use. For evaluating the SPME procedure, program was 36 °C, held for 21 min, then increased at 10 °C/min
water standards containing 200 µg/L of each HAA were prepared to 140 °C, held for 3 min, up to 240 °C at 20 °C/min, held for 5
by adding 50 µL of a standard mixture of 45 µg/mL into 10 mL of min, and finally increased at a rate of 20 °C/min to 280 °C and
Milli-Q water and then sealing them in a 30-mL screw-capped vial. held for 10 min. Carrier gas was hydrogen (32 cm/s at 36 °C),
Barcelona tap water and swimming-pool water samples were and nitrogen was used as makeup gas (50 mL/min). A 30-m DB-
analyzed using the proposed HS-SPME protocol as well as the 17 (50% phenyl, 50% methylpolysiloxane) fused-silica capillary
EPA method 552.2. The samples were collected in 250-mL amber column with 0.25-mm i.d. and 0.25-µm film thickness (J&W) was
glass bottles with PTFE-faced septa and polypropylene screw caps used for confirmation. Injector and detector temperatures were
containing ammonium chloride, avoiding the presence of head- kept at 200 and 330 °C, respectively, and splitless injection mode
space at the top of the bottles. All analyses were performed within (1 min) was used in all analyses. ChromCard version 1.3 software
2 days of sampling. Ammonium chlorine was added as a dechlo- (Fisons Instruments, Spain) was used for data acquisition.
rinating agent to preserve the samples by converting the highly Confirmation of analytes in the more complex sample, swimming-
reactive free chlorine to the less reactive monochloramine. Thus, pool water, was performed by GC/MS.
the free chlorine was prevented from reacting with precursor HS-SPME Procedure. In situ derivatization/HS-SPME was
organic matter to form additional DBPs. optimized using different derivatization reagents such as DES and
Instrumentation. All analyses using SPME procedures were DMS in order to obtain the ethyl and methyl haloacetates prior
carried out with a Varian 3400 CX GC capillary gas chromatograph to the analysis by HS-SPME. Briefly, 10 mL of Milli-Q water
coupled to a Saturn 3 GC/MS ion trap mass spectrometer (Sugar containing 200 µg/L of each compound (total amount of HAAs,
Land, TX). Separations were conducted on a DB-5 MS fused-silica 0.12 µmol) was placed in a 30-mL screw-cap glass vial containing
capillary column, 30 m × 0.25 mm i.d. × 0.25 µm (J&W Scientific, a 10 × 5 mm Teflon-coated stir bar and 5 g (3.5 M) of anhydrous
Folsom, CA), with helium as carrier gas, at a linear velocity of 34 sodium sulfate. After addition of an ion-pairing agent (TBA-HSO4,
cm/s. The column was held at 40 °C for 1 min, ramped at 20 2.3 µmol, as aqueous solution), the vial was closed. One hundred
°C/min to 60 °C, then up to 120 °C at 5 °C/min, held for 3 min, microliters of derivatization reagent (DES, 0.73 mmol, or DMS,
and finally ramped at 25 °C/min to 280 °C and held for 10 min. 1.05 mmol, i.e., high excess) was then injected through the
Desorption time and injection port temperature were set at the septum, and the vial was clamped inside a water-thermostatized
optimum values. bath, which was placed on a hot plate/stirrer. After 5 min at 55
The ion trap mass spectrometer (ITMS) was operated in °C, the fiber was exposed to the headspace above the aqueous
electron ionization (EI) positive-mode using automatic gain control solution for the desired extraction time. Magnetic stirring at 1200
(AGC). For EI experiments, the instrumental parameters were rpm was applied during both stabilization and extraction. Finally,
set at the following values: a filament emission current of 75 µA, the fiber was desorbed in the injection port of the gas chromato-
an electron multiplier voltage of 1850 V, and a modulation graph for 2 min, at different temperatures depending on the fiber
amplitude of 2.5 V, using perfluorotributylamine (FC-43) as coating (splitless injection mode). Several parameters affecting
Analytical Chemistry, Vol. 72, No. 20, October 15, 2000 4867
both derivatization and HS-SPME were then studied: derivatiza- pairing agent. In addition, ethylation was initially used instead of
tion reagent (DMS or DES) and fiber stationary phase type, methylation in order to form relatively high molecular weight
derivatization-extraction temperature (from 35 to 70 °C), deriva- volatile esters, with expected high partition constants on the fiber.
tization-extraction time (up to 60 min), volume of derivatization Optimization of the SPME Conditions. (a) Derivatization
reagent (between 10 and 160 µL of DMS) and amount of ion- Reagent and Fiber Selection. Ethylation of HAAs with DES was
pairing agent (up to 6.6 µmol). Other parameters affecting the initially tested, and the analysis of the derivatives formed using
HS-SPME procedure, such as desorption temperature (280 and HS-SPME with different stationary phases was evaluated to obtain
300 °C), desorption time (up to 2 min), and the effect of ionic high sensitivity and selectivity. Five fibers were tested: PDMS,
strength in the aqueous solution (from 0 to 5 M of anhydrous 100 µm; PA, 85 µm; PDMS-DVB, 65 µm; CAR-PDMS, 75 µm;
sodium sulfate) were also optimized. Possible carryover was PDMS-DVB, 65 µm; and StableFlex DVB-CAR-PDMS, 50/30 µm.
prevented by keeping the fiber in the injector for an additional SPME conditions are described in the Experimental Section. A
time with the injector in the split mode (purge on). Moreover, long extraction time (60 min) was applied to select the fiber
blanks were run periodically during the analysis to confirm the coating, to ensure that a large amount of ethyl derivatives was
absence of contaminants. For optimization, all determinations were formed and extracted. The desorption temperatures were within
performed in duplicate, and the average values are reported. the recommended operating range for each fiber: 250 °C for
Liquid-Liquid Extraction Procedure (EPA Method 552.2). PDMS, 290 °C for PA, 260 °C for PDMS-DVB and DVB-CAR-
Liquid-liquid extraction for the determination of HAAs in tap PDMS, and 280 °C for CAR-PDMS. No carryover on second
water and swimming-pool water was performed in triplicate desorptions was found for any of the fibers, indicating complete
following EPA method 552.27 with minor modifications. Briefly, removal of analytes at these temperatures. The results showed
11 µL of a MtBE solution of 2,3-dibromopropionic acid 22 µg/ that these fibers were not suitable for all the analytes because
mL, as surrogate standard, 3 mL of concentrated sulfuric acid (to only small amounts of MBAA, DCAA, and DBAA ethyl haloac-
obtain pH < 0.5), 12 g of anhydrous sodium sulfate, 3 g of copper etates were detected. Moreover, all fibers showed an extremely
(II) sulfate pentahydrate, and 2 mL of MtBE were added to a 30- broad peak close to those of the TCAA and BCAA ethyl esters,
mL water sample placed in a 40-mL vial. The vials were then sealed which interfered with the determination of these compounds.
with Teflon-faced septa, shaken for 15 min in a rotary mixer, and Since these problems were hard to overcome, methylation was
allowed to stand for 5 min. To derivatize the HAAs, 1 mL of the performed using DMS, and the fiber coating was optimized. The
MtBE extract and 2 mL of methanol/sulfuric acid (9:1) were relative responses obtained for methyl haloacetates using the
transferred to a 10-mL vial, which was placed in a thermostatic fibers are shown in Figure 1. Homogeneous polymer coatings,
water bath at 50 °C for 1 h. After cooling to 4 °C, 5 mL of a CuSO4/ such as PDMS and PA fibers, did not extract HAAs methyl esters;
Na2SO4 solution was added and the mixture was shaken by hand
only small amounts of di- and trihalogenated HAAs derivatives
for 2 min. An aliquot of 300 µL of MtBE extract was transferred
(from 0.03 to 3.7% respect to maximum response area for DBAA
to a 2-mL vial, and 3 µL of a MtBE solution of 1,2-dibromopropane,
with the CAR-PDMS fiber) were extracted. For coatings formed
of 10 mg/L, was added as internal standard. Finally, 1 µL of the
by porous polymeric phases such as PDMS-DVB, CAR-PDMS,
MtBE extract was injected into the GC.
and the dual-coated DVB-CAR-PDMS, the HAAs methyl esters
were successfully extracted (Figure 1). This may be due to the
RESULTS AND DISCUSSION strong retention of the analytes into the pores. Generally, the high
The objective was to develop and optimize both the in situ molecular weight derivatives showed best extraction efficiencies
derivatization and the extraction conditions for the quantification for these three fibers, except TBAA, which showed low sensitivity.
of HAAs from water. To derivatize carboxylic acids, an esterifi- This could be explained by the fact that TBAA undergoes
cation reaction is frequently used. For instance, NaOH or K2CO3 spontaneous decomposition to bromoform6 in aqueous solution
catalyzes in situ methylation of diols, phenols, or even aliphatic
even at 25 °C, or could have undergone thermal degradation
acids with low molecular weight, but cannot be used for direct
during esterification with DMS.12 The presence of bromoform was
analysis of halogenated acids in water, such as HAAs, because
confirmed by identification in the chromatogram. Moreover, peaks
they decompose to halogenated hydrocarbons in acidic or alkaline
corresponding to the decomposition of BDCAA, CDBAA, and
media. Another possibility of in-matrix derivatization of organic
TCAA to the respective halogenated hydrocarbons were also
acids involves the alkylation with dimethyl sulfate12,33 to the
observed in the chromatogram, but the yield of formation was
corresponding methyl ester. The addition of modifiers, such as
low. On the other hand, only the dual-coated DVB-CAR-PDMS
ion-pairing agents, which activate the analytes during derivatiza-
and CAR-PDMS fibers extracted all HAAs, including the mono-
tion, increases esterification yields and thus improves the sensitiv-
halogenated species; CAR-PDMS showed the highest extraction
ity of the procedure.12 Ammonium quaternary salts, such as
efficiency for all the compounds (responses were 1.7-8 times
tetrabutylammonium bromide or tetrabutylammonium chloride,
higher than those obtained with dual-coated DVB-CAR-PDMS
can be used as ion-pairing agents for the analysis of HAAs in water.
fiber). The mean micropore diameter (10 Å) of Carboxen is lower
However, they react with the derivatization reagents, dimethyl
than that of divinylbenzene (17 Å), so it would be ideal for SPME
sulfate or diethyl sulfate, to form halogenated hydrocarbons, which
analyses of small molecules in the C2-C6 range,22 such as HAAs
could compete with HAAs derivatives for the fiber. So, tetrabu-
methyl esters. In terms of selectivity, it should be noted that some
tylammonium hydrogen sulfate (TBA-HSO4) was used as the ion-
additional peaks appeared at the beginning of the chromatogram
(33) Neu, H.-J.; Ziemer, W.; Merz, W. Fresenius’ J. Anal. Chem. 1991, 340, 65- with CAR-PDMS fiber in comparison with those with PDMS-DVB
70. and DVB-CAR-PDMS fibers. However, these peaks did not
4868 Analytical Chemistry, Vol. 72, No. 20, October 15, 2000
Figure 1. Extraction efficiency of five commercial SPME fibers. All recoveries are normalized to the maximum area response obtained. Milli-Q
water containing 200 µg/L of each HAA; DMS, 100 µL; TBA-HSO4, 2.3 µmol; sodium sulfate, 3.5 M; extraction time, 60 min; extraction temperature,
55 °C.
a LOD, limit of detection. b Precisions expressed as RSDs (%). c n ) 5. d n ) 5 replicates × 3 days. e n ) 7 (reagent water spiked between 2.00
and 20.0 µg/L). f The LOD is defined as a level of a compound in a sample yielding a peak in the final extract with a signal-to-noise (S/N) ratio
of approximately five, whichever is greater.
ACKNOWLEDGMENT
reaction yield was obtained using TBA-HSO4 as modifier for the This study was supported by CICYT-Spain project number
in situ methylation with dimethyl sulfate. HS-SPME in conjunction AMB97-0405 and the Pla de Recerca de Catalunya (Generalitat
with GC/ITMS gave good precision; it was linear over 2 orders de Catalunya), project number 1999SGR00049. M.N. Sarrión
acknowledges a Ph.D. fellowship from the University of Barcelona.
of magnitude and the detection limits were at the low ppb level.
The method is proposed as an alternative to the liquid-liquid Received for review April 26, 2000. Accepted July 19,
extraction (EPA method 552.2) for the analysis of HAAs in 2000.
aqueous matrixes containing either low or high HAAs levels. AC000479D
Analytical Chemistry, Vol. 72, No. 20, October 15, 2000 4873